The crystal and molecular structures of the K[Tb^(III)(edta)(H_2O)_3].5 H_2O(edta = ethylenediaminetetraacetic acid) and K_4[Tb^(III)_2(Httha)_2].14 H_2O (ttha =triethylenetetraminehexaacetic acid) complexes have been...The crystal and molecular structures of the K[Tb^(III)(edta)(H_2O)_3].5 H_2O(edta = ethylenediaminetetraacetic acid) and K_4[Tb^(III)_2(Httha)_2].14 H_2O (ttha =triethylenetetraminehexaacetic acid) complexes have been determined by single-crystal X-raydiffraction analyses. The crystal of the K[Tb^(III)(edta)(H_2O)_3].5 H_2O complex belongs toorthorhombic crystal system and Fdd 2 space group. The crystal data are as follows: a = 1.9373(5)nm, b = 3.5429(10) nm, c = 1.2114(3) nm, V 8.315(4) nm^3, Z= 16, M= 630.35, Dc = 2.014 g cm^(-3), m= 3.683 mm^(-1) and F(000) = 5024. The final Rand wR values are 0.0224 and 0.0557 for 3189 [I> 2.0sigma(I)] unique reflections, and 0.0245 and 0.0567 for all 8206 reflections, respectively. The[Tb^(III)(edta)(H_2O)_3]^- complex anion has a nine-coordinated pseudo-monocapped squareantiprismatic structure in which the nine coordinate atoms, two N and seven O come from one edtaligand and three water molecules. The crystal of the K_4[Tb^(III)_2(Httha)_2].14 H_2O complexbelongs to monoclinic system and P 2(1)/n space group. The crystal data are as follows: a =1.1326(3) nm, b = 2.5675(7) nm, C =2.2076(6) nm, bate = 102.943(5) centre dot, V =6.256(3) nm^3, Z =4, M = 1705.26, Dc = 1.802 g cm^(-3), m = 2.611 mm^(-1) and F(000) = 3424. The final R and wR are0.0339 and 0.0667 for 10699 [I>2.0 sigma (I)] unique reflections, and 0.0543 and 0.0741 for all22190 reflections, respectively. The total complex molecule is composed of two close parts instructure.展开更多
The europium heptadentate coordinatively unsaturated (Eu(III)) and the terbium (Tb(III)) 1,4,7,10-tetraazacyclododecane (cyclen) complexes 1 and 2 were used in conjunction with ligand 3 (1,3,5-benzene-trisethynylbenzo...The europium heptadentate coordinatively unsaturated (Eu(III)) and the terbium (Tb(III)) 1,4,7,10-tetraazacyclododecane (cyclen) complexes 1 and 2 were used in conjunction with ligand 3 (1,3,5-benzene-trisethynylbenzoate) to form the supramolecular self-assembly structures 4 and 5;this being investigated in both the solid and the solution state. The resulting self-assemblies gave rise to metal centered emission (both in the solid and solution) upon excitation of 3, confirming its role as a sensitizing antenna. Drop-cased examples of ligand 3, and the solid forms of 4 and 5, formed from both organic and mixture of organic-aqueous solutions, were analyzed using Scanning Electron Microscopy, which showed significant changes in morphology;the ligand giving rise to one dimensional structures, while both 4 and 5 formed amorphous materials that were highly dense solid networks containing nanoporous features. The surface area (216 and 119 m2·g^-1 for 4 and 5 respectively) and the ability of these porous materials to capture and store gases such as N2 investigated at 77 K. The self-assembly formation was also investigated in diluted solution by monitoring the various photophysical properties of 3–5. This demonstrated that the most stable structures were that consisting of a single antennae 3 and three complexes of 1 or 2 (e.g., 4 and 5) in solution. By monitoring the excited state lifetimes of the Eu(III) and Tb(III) ions in H2O and D2O respectively, we showed that their hydration states (the q-value) changed from -2 to 0, upon formation of the assemblies, indicating that the three benzoates of 3 coordinated directly to the each of the three lanthanide centers. Finally we demonstrate that this hierarchically porous materials can be used for the sensing of organic solvents as the emission is highly depended on the solvent environment;the lanthanide emission being quenched in the presence of acetonitrile and THF, but greatly enhanced in the presence of methanol.展开更多
A novel Tb(III) ternary complex Tb(p-BBA)3MAA was synthesized with 4-benzoylbenzoic acid (p-BBA) and methacrylic acid (MAA) as ligands. The complex was characterized by IR, UV-visible, thermogravimetric analysis and f...A novel Tb(III) ternary complex Tb(p-BBA)3MAA was synthesized with 4-benzoylbenzoic acid (p-BBA) and methacrylic acid (MAA) as ligands. The complex was characterized by IR, UV-visible, thermogravimetric analysis and fluorescence spectroscopy. Monitored at 544 nm, the complex displayed wide and strong excitation band at 300–400 nm, which matched well with the 365 nm-emitting UV chip. The complex exhibited excellent green emission at 544 nm (5D4→7F5 transition of Tb3+) under an excitation at 365 nm. Besides, the complex showed high thermal stability. Its intramolecular energy transfer process was further discussed. Fur-thermore, the complex also had higher fluorescence lifetime (1.38 ms) and higher quantum yield (0.372). Finally, electroluminescent properties indicated that when used to fabricate LED with 365 nm UV chip (power efficiency is 18.6 lm/W), the complex remained its favorable optical performance. These results implied that Tb(p-BBA)3MAA could be used as a green phosphor for NUV-based white LED.展开更多
文摘The crystal and molecular structures of the K[Tb^(III)(edta)(H_2O)_3].5 H_2O(edta = ethylenediaminetetraacetic acid) and K_4[Tb^(III)_2(Httha)_2].14 H_2O (ttha =triethylenetetraminehexaacetic acid) complexes have been determined by single-crystal X-raydiffraction analyses. The crystal of the K[Tb^(III)(edta)(H_2O)_3].5 H_2O complex belongs toorthorhombic crystal system and Fdd 2 space group. The crystal data are as follows: a = 1.9373(5)nm, b = 3.5429(10) nm, c = 1.2114(3) nm, V 8.315(4) nm^3, Z= 16, M= 630.35, Dc = 2.014 g cm^(-3), m= 3.683 mm^(-1) and F(000) = 5024. The final Rand wR values are 0.0224 and 0.0557 for 3189 [I> 2.0sigma(I)] unique reflections, and 0.0245 and 0.0567 for all 8206 reflections, respectively. The[Tb^(III)(edta)(H_2O)_3]^- complex anion has a nine-coordinated pseudo-monocapped squareantiprismatic structure in which the nine coordinate atoms, two N and seven O come from one edtaligand and three water molecules. The crystal of the K_4[Tb^(III)_2(Httha)_2].14 H_2O complexbelongs to monoclinic system and P 2(1)/n space group. The crystal data are as follows: a =1.1326(3) nm, b = 2.5675(7) nm, C =2.2076(6) nm, bate = 102.943(5) centre dot, V =6.256(3) nm^3, Z =4, M = 1705.26, Dc = 1.802 g cm^(-3), m = 2.611 mm^(-1) and F(000) = 3424. The final R and wR are0.0339 and 0.0667 for 10699 [I>2.0 sigma (I)] unique reflections, and 0.0543 and 0.0741 for all22190 reflections, respectively. The total complex molecule is composed of two close parts instructure.
基金Science Foundation Ireland (PI awards 13/IA/1865 to T.G. and 13/IA/1896 to W.S.)the Irish Research Council (Postgraduate Scholarship to DC)+1 种基金the European Research Council (CoG 2014 - 647719 to W.S.)the School of Chemistry, Trinity College Dublin.
文摘The europium heptadentate coordinatively unsaturated (Eu(III)) and the terbium (Tb(III)) 1,4,7,10-tetraazacyclododecane (cyclen) complexes 1 and 2 were used in conjunction with ligand 3 (1,3,5-benzene-trisethynylbenzoate) to form the supramolecular self-assembly structures 4 and 5;this being investigated in both the solid and the solution state. The resulting self-assemblies gave rise to metal centered emission (both in the solid and solution) upon excitation of 3, confirming its role as a sensitizing antenna. Drop-cased examples of ligand 3, and the solid forms of 4 and 5, formed from both organic and mixture of organic-aqueous solutions, were analyzed using Scanning Electron Microscopy, which showed significant changes in morphology;the ligand giving rise to one dimensional structures, while both 4 and 5 formed amorphous materials that were highly dense solid networks containing nanoporous features. The surface area (216 and 119 m2·g^-1 for 4 and 5 respectively) and the ability of these porous materials to capture and store gases such as N2 investigated at 77 K. The self-assembly formation was also investigated in diluted solution by monitoring the various photophysical properties of 3–5. This demonstrated that the most stable structures were that consisting of a single antennae 3 and three complexes of 1 or 2 (e.g., 4 and 5) in solution. By monitoring the excited state lifetimes of the Eu(III) and Tb(III) ions in H2O and D2O respectively, we showed that their hydration states (the q-value) changed from -2 to 0, upon formation of the assemblies, indicating that the three benzoates of 3 coordinated directly to the each of the three lanthanide centers. Finally we demonstrate that this hierarchically porous materials can be used for the sensing of organic solvents as the emission is highly depended on the solvent environment;the lanthanide emission being quenched in the presence of acetonitrile and THF, but greatly enhanced in the presence of methanol.
基金supported by the Program for International Science&Technology Cooperation Program of China(2012DFR50460)the National Natural Science Foundation of China(21471111)+3 种基金Shanxi Provincial Key Innovative Research Team in Science and Technology(2012041011)Natural Science Foundation of Shanxi Province(2013011013-2)Program for Science and Technology Development of Shanxi(20140321012-01)Excellent Scientist Fund in Neimenggu,China
文摘A novel Tb(III) ternary complex Tb(p-BBA)3MAA was synthesized with 4-benzoylbenzoic acid (p-BBA) and methacrylic acid (MAA) as ligands. The complex was characterized by IR, UV-visible, thermogravimetric analysis and fluorescence spectroscopy. Monitored at 544 nm, the complex displayed wide and strong excitation band at 300–400 nm, which matched well with the 365 nm-emitting UV chip. The complex exhibited excellent green emission at 544 nm (5D4→7F5 transition of Tb3+) under an excitation at 365 nm. Besides, the complex showed high thermal stability. Its intramolecular energy transfer process was further discussed. Fur-thermore, the complex also had higher fluorescence lifetime (1.38 ms) and higher quantum yield (0.372). Finally, electroluminescent properties indicated that when used to fabricate LED with 365 nm UV chip (power efficiency is 18.6 lm/W), the complex remained its favorable optical performance. These results implied that Tb(p-BBA)3MAA could be used as a green phosphor for NUV-based white LED.
